JPS60198533A - Diazo copying sheet for forming intermediate original - Google Patents

Abstract

PURPOSE:To enhance color formation characteristics, an image light interception degree, etc., by forming each in a specified amt., a photosensitive layer contg. a diazo compd., an acid stabilizer, and 2 kinds of couplers represented by each specified formula on one side of a sheet support. CONSTITUTION:A diazo copying sheet for forming an intermediate original is obtained by forming on one side of a sheet support a photosensitive layer contg. a diazo compd., an acid stabilizer, and a coupler A represented by formula I , R1 being 1-3C alkyl, carboxy, amide, or aimnobenzoyl, and a coupler B represented by formula II, R2 being O, S, SO, or SO2, in an A/B molar ratio of 1:(0.25- 0.65), and in a acid stabilizer/(A+B) weight ratio of (0.15-0.45):1.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a diazo second original drawing sheet. More specifically, the present invention relates to a sheet for diazo second original images which shows almost no deterioration in color development over time and can be developed by both dry and semi-dry development methods.

Technical background Diazo second original drawing sheets are widely used when copying industrial drawings to prevent the original drawings from being soiled or to save the trouble of replacing the original drawings when making drawing corrections. There is.

As a developing method for forming a second original image on a diazo second original image sheet, a dry method using ammonia gas is known. However, the apparatus 4 for carrying out this dry method had drawbacks such as requiring a large chassis and exhaust duct, and in addition, leakage of ammonia odor was inevitable. In order to eliminate these drawbacks, a so-called semi-dry method was developed in which development is carried out by applying a small amount of alkaline developer to the diazo photosensitive surface of the second original drawing sheet, and this method is used to develop office documents. It has come to be widely used in the field of copying and copying industrial drawings. However, the conventional second original sheet suitable for the dry developing method is not suitable for the semi-dry method, and the conventional second original sheet suitable for the semi-dry method is not suitable for the dry method, so both developing methods are used. When used together, there was an inconvenience that two types of second original drawing sheets had to be prepared. This point will be explained in more detail below.

Generally, the diazo second original sheet is used for the purpose of further forming copies of the original, and therefore, the colored dye image formed thereon must have as low ultraviolet transmittance as possible. is required. For this reason, in conventional sheets for second original drawings, a diazo compound component and an acetamide derivative or a phenol derivative are widely used as a yellow dye coupler that reacts with the diazo compound component to form a yellow azo dye. However, since the visual density of such an image using only yellow dye is too low, it becomes difficult to see the image when making additions to the second original drawing, making the work difficult.

In order to overcome these drawbacks, it is known that as a coloring image forming material for a second original sheet, a material is used in combination with a coupling component that reacts with a diazo compound component to form a brown dye. In such a second original drawing sheet, an acid stabilizer is used in combination to suppress the reaction between the diazo compound component and the coupling component during storage.

As mentioned above, the conventional photosensitive layer for second original image containing a diazo compound component, a yellow dye-forming coupler, a brown dye-forming coupler, and an acid stabilizer has the following problems. In other words, there is a large difference in the coupling reaction rate between the yellow dye-forming coupler and the brown dye-forming coupler with the diazo compound component, and the degree of this difference is even greater when dry development is used and when semi-dry development is used. The problem is that they are significantly different. For this reason, when the composition of the second original sheet photosensitive layer is used in the dry development method,
And when used in a semi-dry development method, it was necessary to change the quality accordingly to maintain the quality of the resulting image at a desired level.

Furthermore, in the conventional photosensitive layer of the second original sheet, when an acid stabilizer is used in combination, it is difficult to maintain the coupling color-forming activity of the coupling component over a long period of time.

OBJECTS OF THE INVENTION An object of the present invention is to provide a diazo second original sheet which is compatible with both dry and semi-dry development methods and is capable of forming images of desired quality.

Another object of the present invention is to provide a sheet for diazo second original drawings that exhibits almost no deterioration in coloring properties over time.

Structure of the Invention The diazo second original sheet of the present invention comprises: a sheet-like support; and a photosensitive layer formed on one surface of the support and containing a diazo compound component, a coupling component, and an acid stabilizer. , wherein the coupling component has the following general formula (I) and [wherein R1 is an alkyl group having 1 to 3 carbon atoms, a carboxyl group, an and group, and an aminobenzoyl group] Represents a selected member, R2 is -o -, -s
represents one member selected from -, -5o- and -502- groups.
The acid stabilizer is contained in a molar ratio of 0.6 s, and the ratio of the amount of M to the total amount of the couplers A and B is within the range of 0.15:1 to 0.45:1. It is characterized by the following.

DESCRIPTION OF SPECIFIC EMBODIMENTS OF THE INVENTION In the diazo second original sheet of the present invention, the sheet-like support is usually paper, a plastic film, e.g.
It is formed from polypropylene film, etc.

A photosensitive layer is formed on one side of the support. This photosensitive layer is
It contains a diazo compound component, a coupling component, and an acid stabilizer.

The coupling component is a compound represented by the following general formula (I): Coupler A consisting of one type of compound and the following general formula (■): [However, in the above formula, R2 is -o-, -s-, -so
- or -802- group].

Coupler A consisting of a compound of general formula (I) is a coupler that forms a yellow dye, and coupler B consisting of a compound of general formula (I[) is a coupler that forms a brown dye.

The molar ratio of coupler A and coupler B is 1:0.
25~1:0.65, preferably 1:o, ao~
1: within the range of 0.60.

If the molar ratio of coupler A to coupler B is greater than 0.25, the tone of the image obtained by development will be too yellowish and the visual density will be insufficient. Furthermore, when the molar ratio of coupler A and coupler B becomes smaller than 1:0.6 s, the ultraviolet transmittance of the resulting colored image increases, making it unsatisfactory as an image of the second original image.
This results in a disadvantage that the deterioration of color development over time becomes significantly large.

The weight ratio of the acid stabilizer to the total amount of couplers A and B is 0.15:1 to 0.4s:1.
, preferably within the range of 0.2:t to 0.4:1. If this weight ratio is smaller than 0.15:1, the stabilizing effect of the photosensitive layer will be insufficient, the pre-coupling phenomenon of the coupling component will be large, and background coloration will occur before use. A clear image cannot be obtained even after development. Furthermore, if the weight ratio becomes larger than 0.45:1, the stabilizing effect of the photosensitive layer becomes excessively large, and the reaction rate between the coupling component and the diazo compound component becomes excessively low. This also has the disadvantage that the color-forming activity of the coupler component is excessively reduced.

As described above, in the composition of the photosensitive layer of the present invention, the blending ratio of coupler A1, coupler B1, and acid stabilizer is extremely important, and these must be strictly defined within the ranges described above. If these blending ratios are inappropriate, it will not be possible to obtain a useful diazo second original sheet that can achieve the object of the present invention.

The diazo compound component used in the diazo second original drawing sheet of the present invention can be selected from those used in conventional diazo second original drawing sheets using two-component coupling components. Such a diazo compound component is, for example, N
-ethylaminobenzenediazonium zinc chloride salt, 4-
Mol 7 Olinobenzenediazonium boron tetrafluoride salt, p
-N,N-diethylaminobenzenediazonium boron tetrafluoride salt, 4-morpholino-2,5-dibutoxybenzene-diazonium boron tetrafluoride salt, and 4-pyrrolidino-3-methylbenzenediazonium boron tetrafluoride salt It contains at least one species.

The compound of general formula (I) constituting coupler A is selected from, for example, 3-acetamidophenol, 3-N-4'-aminobenzoylaminophenol, m-hydroxyphenylurea, and 3-hydroxyoxanilic acid. .

The compound of general formula (II) constituting coupler B is:

For example, 2.2',4.4'-tetrahydroxydiphenyl sulfide and 2.2',4.4'-tetrahydroxydiphenyl sulfide.

The acid stabilizer may be one used in conventional sheets for diazo second originals, but it may be composed of one or more selected from citric acid, sulfosalicylic acid, oxalic acid, phosphoric acid, tartaric acid, etc. Ru.

The photosensitive layer of the present invention may contain, in addition to the above-mentioned diazo compound component, coupling component, and acid stabilizer, a binder for binding these components and adhering them to the surface of the support. The binder may be made of at least one selected from cellulose derivatives, vinyl chloride-vinyl acetate copolymers, polyvinyl acetates, polyester resins, and polyacrylic acid ester resins. good.

The photosensitive layer may also contain a desired amount of storage stabilizer (for example, salts such as aluminum sulfate and zinc chloride). Additionally, the photosensitive layer may contain desired amounts of inorganic fine particles, such as silica and kaolin.

Generally, in the diazo second original sheet of the present invention, the weight of the photosensitive layer is preferably within the range of 2.0 to 6.0 t/m2, and the weight of the diazo compound component is 0.2 to 6.0 t/m2.
It is preferably within the range of 1.2 f/m'', and further,
The total amount of coupler A and coupler B is 0.2 to 1
．． It is preferably within the range of 2f/m2.

In order to produce the sheet for diazo second original drawings of the present invention, an organic solvent coating solution containing the desired components is prepared, and this coating solution is applied onto one side of a sheet-like support using a conventional coating method. That is, it is applied by a roller coating method, a spray method, a brush coating method, and then dried. The coated surface of the sheet-like support is coated with a resin made of polyester resin, acrylic resin, styrene-butadiene resin, or urethane resin.
, 2 to 2.0 f/m2 of precoat layer may be formed.

In addition, as organic solvents for preparing coating liquids, easily volatile methyl alcohol, ethyl alcohol, methyl ethyl ketone 1,
Alternatively, methyl isobutyl ketone, etc. can be used.

The features and effects of the present invention will be specifically explained below using examples.

Example 1゜ A coating liquid having the following composition was prepared.

p-N,N-diethylaminobenzene-diazonium boron tetrafluoride salt 3fm
-Hydroxyphenylurea・・kawa・2f2, 2'
, 4, 4'-tetrahydroxydiphenyl-sulfide... 1.31 Sulfosalicylic acid - Old... 1F Cellulose acetate propionate (CAP 482-0.5, Kodak! J Ri...
15F fine particle silica (Thyroid 404, manufactured by Fuji Davison) 5f methylene blue ° 0.1f methyl alcohol
...701 The above coating liquid was applied uniformly onto one side of a polyethylene terephthalate film (thickness: 50 microns) having a pre-coated layer made of urethane resin using a Mayer bar, and heated at 100°C in a hot air circulation dryer. , 2 minutes,
It was dried to form a photosensitive layer having a weight of 3 f 7 m 2 to produce a second diazo original sheet.

The original drawing sheet was layered on the photosensitive layer of the test sheet taken from this second original drawing sheet, and this was developed using a commercially available dry type diazo copying machine (5M-1500 manufactured by Ricoh Co., Ltd.) to develop its dry color. The sex was measured.

In addition, other test sheets were developed using a commercially available semi-dry copying machine (PD-113, manufactured by Bunshodo Co., Ltd.), and their semi-dry coloring properties were measured. Furthermore, another test sheet was coated with a light-shielding film (black).
The sample was packaged and left indoors for 6 months, and its color development during dry and semi-dry development was measured in order to examine changes over time.

The above test results are shown in Table 1.

However, when measuring dry color development, use 25% as a developer.
% (heavy weight) ammonia aqueous solution is used and the copy speed scale of the copying machine is set to 30, and the image density is measured, and the ratio (a) of this image density to the fully colored image density is determined as the dry color development. Gender is indicated.

In addition, when measuring semi-dry color development, a commercially available alkaline organic developer solution (PD Activator, manufactured by Bunshodo Co., Ltd.) was used as the developer, the copy speed scale of the copying machine was set to 10, and the development time was approximately 30 seconds). The resulting image density was measured, and the ratio (%) of this image density to the density of the fully colored image was taken as semi-dry coloring property.

Furthermore, the semi-dry light shielding property was measured as follows.

That is, the fully colored second original image sheet is placed on a commercially available photosensitive paper, a normal copying operation is performed with the scale of a semi-dry type copying machine set to 10, the density of the obtained image is measured, and the density of the image obtained is measured on the commercially available photosensitive paper. The semi-dry light shielding property was expressed as the ratio of the fully colored image to the original size (@).

Furthermore, the background coloration of the test sheet that had been left indoors for 6 months was measured as follows. That is, we collected the Dhlin from the test sheet that had been left indoors for 6 months and added it to D'.
Then, take the Dmin and Dmax of the sheet before leaving it,
When this was expressed as D □ and Dnlax, the ground coloring property of the test sheet was calculated using the following formula.

D' - D packed.

Background color development (a)=X100 D'max-D: n1n Example 2 The process described in Example 1 was carried out. However, the composition of the coating liquid was as follows.

4-morpholinobenzenediazonilla penta-tetrafluoroborate salt...3t3-acetamidophenol...1.8F2, 2',
4,4'-tetrahydroxydiphenyl-sulfoxide 1.4f sulfosalicylic acid
・・・・・・ 0.7f cellulose globionate ・
・・・・・・ 72 Polyvinyl acetate °° group-71 Colloidal silica ・・・・・・ 82 Methylene blue ・・・・・・ 0.1f Methyl alcohol ・・・・
...70f This coating liquid was applied to one side of semi-transparent synthetic paper (Yubotrace, manufactured by Tamako Yuka Synthetic Paper Co., Ltd.) coated with a polyester resin, and dried in a hot air circulation dryer for 90 minutes.
Drying was carried out at 0°C for 2 minutes to produce a second original drawing sheet having a photosensitive layer weighing 3t/m". The thickness of this sheet was 75 microns and the transparency was 35%.

The results of the dry and semi-dry development tests are shown in Table 1.

Comparative Examples 1 to 4 In each of Comparative Examples 1 to 4, the steps described in Example 1 were carried out. However, in Comparative Example 1, 3f m-hydroxyphenylurea was used in place of 3-acetamidophenol, and 2,2',4,4'-tetrahydroxydiphenyl sulfoxide was used in place of 2,2',4,4'-tetrahydroxydiphenyl sulfoxide. KSo, a t(7)
2.2',4.4'-tetrahydroxydiphenyl sulfide was used. Moreover, in Comparative Example 2, 0.8 f m-hydroxyphenylurea was used instead of 3-acetamidophenol, and 2.
52 of 2,2',4,4'-tetrahydroxydiphenyl sulfide was used.

Furthermore, in Comparative Example 3, sulfosalicylic acid was 2. O
f was used.

Furthermore, in Comparative Example 4, 0.3 f of sulfosalicylic acid was used.

The results of the dry and semi-dry development tests are shown in Table 1.

As is clear from Table 1, the performance of the photosensitive layers of Comparative Examples 1 to 4 was unsatisfactory, but the photosensitive layers of Examples 1 and 2 had
All showed satisfactory performance.

Effects of the Invention The sheet for diazo second original images of the present invention exhibits sufficiently satisfactory color development, image shading degree, and stability over time in both dry and semi-dry development, and is highly practical as a second original image sheet. can be formed.

patent applicant Oji Paper Co., Ltd. patent application agent Patent Attorney Akira Aoki Patent Attorney Kazuyuki Nishitate Patent attorney Akira Yamaguchi Patent attorney Masaya Nishiyama

Claims (1)

[Claims] 1. A sheet-like support, and a photosensitive layer formed on one side of the support and containing a diazo compound component, a coupling component, and an acid stabilizer; The coupling component has the following general formula (I) and (■
): [However, in the above formula, R1 represents one member selected from an alkyl group having 1 to 3 carbon atoms, a carboxyl group, an and group, and an aminobenzoyl group, and R2 is -o-
, -s-, -5o- and -502- groups] Coupler A and Coupler B each consisting of one or more compounds shown in the following formula: 1: 0.25 to 1:
0.65 molar ratio, and the weight ratio of the acid stabilizer to the total amount of the couplers A and B is within the range of 0.15:1 to 0.4 s:t. A sheet for diazo second original drawings. 2. The diazo compound component is N-ethylaminobenzenediazonium zinc chloride salt, 4-morpholinobenzenediazonium boron tetrafluoride salt, p-N,N-diethylaminobenzenediazonium boron tetrafluoride salt, 4-morpholino-2 , 5-dibutoxybenzene-diazonium boron tetrafluoride salt, and 4-pyrrolidino-3-methylbenzenediazonium boron tetrafluoride salt, as described in claim 1. Diazo second original drawing sheet. 3. The coupler A is 3-acetamidophenol, 3-N-4'-aminobenzoylaminophenol,
The diazo second original drawing sheet according to claim 1, comprising at least one selected from m-hydroxyphenylurea and 3-hydroxyoxanilic acid. 4. The coupler B is 2, 2', 4, 4'-
Tetrahydroxydiphenyl sulfide, 2, 2',
4,4'-Tetrahydroxydiphenyl sulfoxide and 2,2',4,4-tetrahydroxydiphenyl sulfoxide, comprising at least one compound selected from Diazo second original drawing sheet. 5. The diazo second original sheet according to claim 1, wherein the acid stabilizer comprises at least one compound selected from citric acid, sulfosalicylic acid, oxalic acid, phosphoric acid, and tartaric acid. 6. Claim 1 in which the photosensitive layer contains a binder
Sheet for the second diazo original drawing described in section. 7. Claim 6, wherein the binder consists of at least 1"m selected from cellulose derivatives, vinyl chloride-vinyl acetate copolymers, polyvinyl acetates, polyester resins, and polyacrylate resins. A sheet for a second diazo original image according to claim 1. 8. A sheet for a second diazo original image according to claim 1, wherein the weight of the photosensitive layer is within a range of 2.0 to 6.0 f/m2. The weight of the diazo compound component is 0.2 to 1.2f
The diazo second original drawing sheet according to claim 1, which is within the range of /m2. 10. The total weight of couplers A and B is 0.2
Claim 1, which is within the range of ~1.2 f/m'
Sheet for the second diazo original drawing described in section.